Conversion of hydrocarbons



Jan. 30, 1940. H. v. ATWELL.

CONVERSION 0F HYDROCARBONS Filed May 1l, 1937 l NNN W QN Patented Jan. 30, 1.940

. [UNITED STATES PATENT oFFlCE l L l 2,188,688 1 CONVERSION F HYDRocARoNs Harold V.' Atwu, white Plains, N. Y., asignor to Process Management Company, Inc., New York, N. Y., a corporation'of Delaware Application May 11, 1987',seria1-N0. 141,899

merization zone where they are subjected to con- 1 ditions of catalytic polymerization in the pres-' ence of an active polymerization catalyst to effect the polymerization of normally gaseous yoleiins in the presence vof the inert gas andthe water vapor. An inordinate rise in temperature of the catalytic surface .and the resultant dehydration 'of the catalystfis avoided in the continuous conversion operation because of the presence of the inert gas and water vapor in the products of the'controllcd oxidation phase of the process.

In accordance with thepresent invention, normaly gaseous hydrocarbon gases consisting essentially or principally of saturated hydrocarbons, such as natural gas, or such 'as obtained, for example, fromv the cracking of hydrocarbon fluids,

are preheated to a temperature sufficiently high v to initiate the controlled oxidation reaction in the presence .of` controlled amounts of an oxygencontaining gas, 'for example air or an oxide of nitrogen such as `NO2 capable of yielding substantial quantities of an inert gas, and the preheated gasesare passed into a reaction zone, such asan enlarged reaction chamber, wherein the' controlled oxidation reaction takes place. The

40 oxygen-containing gas is added inr quantitiesl which are sufficient to effect the dehydrogenation reaction but insufficient to effect complete oxidation of the saturated hydrocarbons, thereby forming substantial quantities of' unsaturated hydrocarbons, inert gas and water vapor.

subjected to catalytic polymerization in the presence of vany active polymerization catalyst,v for exl ample phosphoric acid, aluminum chloride, alumfina on silica, etc., whereby normally gaseous' olens are converted to normally liquid hydrocarbons. In subjecting the unsaturatedhydrocargvbons resulting yfrom the controlled oxidation to The reaction products `leaving the dehydrogenation zone are cooled to a` temperature favorable to the catalytic polymerization reaction and`v are.'

(cl. 19e-Lio) kcatalyst can be controlled to a largedegree by judicious control of the quantity of air/ added to the oxidation zone. Although it is my intention 16 to restrict the oxidation reactionA to one of. partial dehydrogenation, smallamounts of alkyl-oxides resultingY from side reactions will be produced. This iszregarded as an advantageto -my process because of the promotingr eiect these oxides exert 20 upon the subsequent polymerization reaction.

Reaction products leaving the polymerization zone are subjected tofractionation to separate a normally liquid hydrocarbon fraction suitable for ruse as motor fuel. `The remaining reaction 25 products arefurther'fractionated to separate a normally gaseous fraction predominating in C8 and C4 hydrocarbons, which is conducted tothe v dehydrogenating or controlledr oxidation zone.

Theiinvention will be more fully understood 30y lcule,. such as lobtained' in the stabilization of Anatural gasoline or resulting fromthe cracking ofhydrocarbon fluids is' drawn from aV source of supply,` not shown, through line l, controlled by valveZ, and Vforced by the pump l3 through 1in'e`5', 45

regulated'rbyvalve' 4, tothe heatingcoil 6 in a furnace '1;'v Anv 'oxygen-containing gas,` forv example air, is."drav`vn'n from an outside' source throughline 8 and forced by pump 9through` line I0, controlled'by valve i l I, intoline 5 wherein it '50' commingles with the'ch'arge enteringpreheating coil t in furnace 1. In coil 6the hydrocarbonv gases inv admixture with the controlled amounts ofr theoxygen-containing gasY are broughty to a terrmerature of vlo-1400o E. and.preferablyabout 65 lthe charge.

atmospheric to about pounds is to be prei ferred. The preheated gaseous mixture leaving coil 6 is passed through line I2 controlled by valve I3 into the enlarged reaction chamber I4 wherein partial dehydrogenation of the charge takes place. Although I have selected air as a preferred agent for carrying out the primary step of the process, the invention is in no wise limited to the use of this gas. be enriched with oxygen above the normal content of air, or the oxygen content may be lowered by dilution with an inert gas or by any other suitable means. Other oxygen-containing gases capable of liberating required quantities of inert gas during the subsequent reaction may suitably be used; for example, an oxide of nitrogen such as NO2. carefully controlled amounts to effect partial dehydrogenation of the charge in reaction chamber I4 and yet avoid complete oxidation of the charge. Although in the present example describing my invention, the dehydrogenation reaction will be `initiated to a certain extent in coil 6 and completed in the enlarged reaction chamber I4, it should be understood that the invention isnot limited to the use of a reaction chamber for'this phase of the reaction and that the dehydrogenation reaction may be completed in a coil instead; furthermore, if desired, the dehydrogenation reaction may be initiated and completed in a single coil. When proper operating conditions i. are maintained in chamber I4 a partial dehydrogenation of a substantial portion of the saturated charge will take place with the formation of unsaturated hydrocarbons having essentially the same number of carbon atoms to the molecule as raaction favored in the reaction zone I4 is not readily determined, it is believed to be a simple breaking of hydrogen-to-carbon links, with the resultant formation of an unsaturate, a water -molecule and residual inert gas from the oxygencontaining gas added. It is not my intention, however, to limit the controlled oxidation phase of my process to this type of reaction. Conditions of operation may well result in more complicated reactions and the formation of normally gaseous unsaturates having either more or less carbonatoms to the molecule than the hydrocarbon gases charged to the system. Operating conditions vary to a certain degree with composition of the charge, severer conditions being required with an increase in proportion of the light hydrocarbon constituents in the charge. type of operation would be to maintain the reaction chamber under a low pressure preferably substantially atmospheric. The temperaturel may range from 700 to 1500 F. and preferably about 1300 F. Addition of controlled amounts of air is made in such lquantities that there will be at least 30% by volume and no more than 80% by volume, and preferably about 55% by volume of air in themixture entering reaction chamber I4.

If an oxygen-containing gas other than air is used, controlled additions of this gas should be made to insure an equivalent oxygen content in .the mixture entering the reaction chamber I 4.

When air is used it may The oxygen-containing gas is added in Although the exact nature of thev A preferred ing furnace 1 leads to line I2 entering reaction chamber I4. By suitable manipulation of valves 4, I3 and I5, a part of the charge may by-pass the preheating coil 6 whereby a desired portion of the charge will flow through line I6 controlled by valve I5 into transfer line I2 in order to closely control the composition of the charge to the reaction chamber and the temperature therein. Reaction products comprising -unsaturated hydrocarbons, water'vapor, nitrogen, small amounts of oxygenated compounds and unconverted charge, are conducted from the reaction chamber I4 through line I'I controlled by valve I8 to a heat exchanger I9 wherein theproducts of controlled' oxidation are subjected to indirect heat exchange with a cooling medium which lmay suitably be the fresh charge to the system. Additional cooling means of indirect exchange not shown in the drawing may be resorted to if necessary. Inert gas, or Water vapor, or unsaturated hydrocarbons or a suitable mixture of any two or all iof these may be passedvthrough linev 20 controlled by valve 2l from an outside source,

not shown, through line 22 and discharged directly into line I1 for the purpose of additional cooling and additional control, if desired, of conditionsl in the subsequent phase of the process.

hereinafter described in detail. The temperature ofthe products of dehydrogenation leaving exchanger I9 will have been reduced to 200-500 F., preferably 30D-400 F., and are conducted throughline 23 to compressor 24 wherein the stream is brought to a pressure of 50y to 500 pounds and preferably about 100 to 200 pounds, and conducted through line 25 to catalytic polymerization chambers' 25. Line 25 enters the top `of one of two catalytic polymerization chambers.

The stream of gases and vapors flowing `downward through the first polymerization chamber isl withdrawn from the bottom thereof andconducted through line 26 to the top of the second chamber. Although the catalystv chambers in the illustrative description of my process are shown to be .two in number and connected in series, it is to be understood that my invention is not limited to any specic number of catalyst `chambers nor is it restricted to the series arrangement shown. A preferred arrangement Wouldrbe the use of a plurality of catalytic polymerization chambers of which a single chamber or several'chambers, connected in parallel or in series as shown are used in rotation. n

In the catalytic polymerization chambers 26 the products are contacted with an active polymerizationl catalyst such as phosphoric acid. Ordinarily this catalyst is in a solid state,` such as a mixture of phosphoric acid and fullers earth, suitably disposed in the chamber to effect intimate contact between the gases and the catalyst.

While phosphoric acid is preferred, it is to be understoodthat other polymerizing catalysts such as aluminum chloride, sodium aluminum chloride, alumina on silica, sulfuric acid, or similar catalysts may be used. It is intended that in the polymerizing zone 26 a major portion ofthe unsaturated or olefin hydrocarbons be polymerized to normally liquid hydrocarbons, preferably Within. the gasoline boiling range. polymerization phase of the operation-is effected at a temperature of `I300-600 F. and preferably about 40G-500 F. and at a pressure of 50 to 500 pounds, preferably about 100-200 pounds.

tained by judicious control of the cooling effected The catalyticl The desired conditions of temperature and pressure in the-catalytic polymerization zone 26 are main` aid materially in preventing overheating of the catalyst surface. .The quantities of inert gas and watervapor in the reaction products entering the catalytic chambers 26 and ,therefore the permissible vconditions of the polymerization catalyst can be controlledby judicious regulation of the quantity of air admitted through line I0 into coil 6 while still remaining within the desired limits set for the dehydrogenation reaction. l y

Polymerization lproducts leave the second chamber of thecatalytic polymerization chamybers 26 through line 2I and pass through ythe heat exchanger 28, wherein they may be cooled if so desired, and are thence passed vthrough line 29 to `fractionator 30 wherein the products are fractionated to lsepara-te a normally liquid fracktion `consisting of hydrocarbons boiling within the gasoline boiling range and water, which is drawn from the bottom of fractionator 30 throughk line 3| controlled by valve 32 and eliminated from the vsystem as the iinal product.`

The remaining normally gaseous reaction products are conducted from thek top -of fractionator 30, through line 33 to fractionator 34 wherein a normally gaseous fraction predominating in C3 and C4 hydrocarbons is' condensed and separated from the remaining gaseous products and withdrawn through line 35 controlled by valve 44 and recycled bypump 36 through line 31 to join the fresh charge entering the system. All or any part of the normallygaseous hydrocarbons condensed in fractionator'34 and withdrawn therefrom through lineA 35 may, by' suitable manipulation of valves 44 and 43, be withdrawn from the system through liney 42. yIf desired, operation of fractionator 34 `may be carried on in such a manner that any part or substantially all of the C2 hydrocarbons are condensedand separated together with the fraction predominating in C3 and C4 hydrocarbons. Remaining gaseous products comprisingl hydrogen, nitrogen, and hydrocarbons of lessentially less than two or three carbon atomsfper molecule leave fractionator 34 through line 38 controlled'by valve 39 land are eliminated from` the system.l By regulation of valves 39 and 40 all or any part of the gases leaving fractionator 34 may, if desired, be passed through line 4| and into line 22 wherein they may yoptionally be mixed with vinert material from an outside source, referred to above, be-

fore being discharged into the products of contion products and in maintaining the operating conditions of the catalytic material in chambers f As an example of thel operation of the invention, a gas consisting predominantly of propane mixed with an equal volume of air and heated to 1300 F. in coil 6 isy passed into the enlarged reaction chamber |4 wherein it isv maintained at this temperature and substantially `atmospheric pressure.L The resulting products in passing through condenser l@ are cooled to 300 F., and are subsequently compressed to 150 pounds by compressor 24 and subjected to catalytic polymerization in chambers 26 in the presence of a with recycling of unconverted "gases approxi-` mately %,of the normally gaseous hydrocarbons charged is concerted ultimately into liquid polymers Within the gasoline boiling range hav-` ing an octane number of to 85,.H

Many modifications and vvariations of the invention as hereinset forth may be made without departing from the spirit and scope thereof` and therefore only )such limitations should beimposed as are indicated in .the appended claim. I claim:

The method of converting normally gaseous hydrocarbons to normally liquid products by "contact, thereof at elevated temperature with a ypolymerization catalyst whose activity is im-.

paired by dehydrationv and overheating which comprises mixing a gas consistingv essentially of saturated hydrocarbons and' predominating in hydrocarbons having more than two carbon f atoms perv molecule with an oxygen-containing gas in an amount sucient to effect substantial dehydrogenation of said saturated hydrocarbons o but insufficient to effect complete oxidationv of said gas, thereafter heating the resulting mixture to elevated temperatureto initiate and carry to completion the dehydrogenation reaction of said oxygen and said saturated gases to eiect the formation therein of a substantial proportion Aof normally gaseous unsaturated hydrocarbons and inert gaseous reaction products including steam,

cooling said reaction products to a temperaturev not substantially greater than 500 F., thereafter passing all the said products of said dehydrogenation treatment together with unconverted constituents into contact at elevated temperature not substantially greater than 600 F. with said polymerization catalystwhose activity is impaired by dehydration .and overheating to effect conversion `of unsaturated hydrocarbons to normally liquid products.

' o HAROLD V. ATWELL. 

